U.S. patent application number 11/127623 was filed with the patent office on 2005-12-08 for transparent amorphous polyamides based on diamines and on tetradecanedioic acid.
Invention is credited to Blondel, Philippe, Bussi, Philippe, Linemann, Annett.
Application Number | 20050272908 11/127623 |
Document ID | / |
Family ID | 35449914 |
Filed Date | 2005-12-08 |
United States Patent
Application |
20050272908 |
Kind Code |
A1 |
Linemann, Annett ; et
al. |
December 8, 2005 |
Transparent amorphous polyamides based on diamines and on
tetradecanedioic acid
Abstract
The present invention relates to a transparent amorphous
polyamide which results from the condensation of at least one
diamine chosen from aromatic, arylaliphatic and cycloaliphatic
diamines, of tetradecanedioic acid or of a mixture comprising at
least 50 mol % of tetradecanedioic acid and at least one diacid
chosen from aliphatic, aromatic and cycloaliphatic dicarboxylic
acids. The invention also relates to a composition comprising, by
weight, 1 to 100% of the preceding polyamide and 99 to 0% of a
semicrystalline polyamide. The invention also relates to the
objects composed of the composition of the invention, such as
panels, films, sheets, pipes, profiles or objects obtained by
injection moulding. The invention also relates to objects covered
with a transparent protective layer composed of the composition of
the invention.
Inventors: |
Linemann, Annett;
(Nassandres, FR) ; Bussi, Philippe; (Versailles,
FR) ; Blondel, Philippe; (Bernay, FR) |
Correspondence
Address: |
Arkema Inc.
2000 Market St.
Philadelphia
PA
19103
US
|
Family ID: |
35449914 |
Appl. No.: |
11/127623 |
Filed: |
May 12, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60603214 |
Aug 20, 2004 |
|
|
|
Current U.S.
Class: |
528/310 |
Current CPC
Class: |
Y10T 428/139 20150115;
C08G 69/26 20130101; C08G 69/265 20130101 |
Class at
Publication: |
528/310 |
International
Class: |
C08G 069/08 |
Foreign Application Data
Date |
Code |
Application Number |
May 14, 2004 |
FR |
04.05259 |
Claims
What is claimed is:
1. A transparent amorphous polyamide comprising the condensation
product of: a) at least one diamine selected from the group
consisting of aromatic diamines, arylaliphatic diamines, and
cycloaliphatic diamines; b) tetradecanedioic acid or of a mixture
comprising at least 50 mol % of tetradecanedioic acid and at least
one diacid selected from the group consisting of aliphatic
dicarboxylic acids, aromatic dicarboxylic acids, and cycloaliphatic
dicarboxylic acids.
2. The polyamide of claim 1 wherein said condensation product is
formed in the presence of a catalyst.
3. The polyamide according to claim 1, in which the diamines have
the following formula: 2in which R1 to R4 represent identical or
different groups chosen from a hydrogen atom or alkyl groups of 1
to 6 carbon atoms and X represents either a single bond or a
divalent group composed: of a linear or branched aliphatic chain of
1 to 10 carbon atoms, of a cycloaliphatic group of 6 to 12 carbon
atoms, of a linear or branched aliphatic chain of 1 to 10 carbon
atoms substituted by cycloaliphatic groups of 6 to 8 carbon atoms,
or of a group of 8-12 carbon atoms composed of a linear or branched
dialkyl with a cyclohexyl or benzyl group.
4. The polyamide according to claim 1, wherein the tetradecanedioic
acid is replaced by a mixture comprising at least 70 mol % of
tetradecanedioic acid and at least one diacid selected from the
group consisting of aliphatic dicarboxylic acids, aromatic
dicarboxylic acids, and cycloaliphatic dicarboxylic acids.
5. A blend composition comprising, by weight, 1 to 100% of the
amorphous polyamide of claim 1 and 99 to 0% of a semicrystalline
polyamide.
6. The blend composition of claim 5 wherein said blend occurs in
the molten state and in the presence of a catalyst.
7. The composition according to claim 5, further comprising one or
more additives selected from the group consisting of reinforcing or
non-reinforcing fillers, heat or UV stabilizers, internal or
external lubricants, plasticizers, flame retardants, pigments and
dyes, conductive or static-dissipative fillers, impact modifiers,
and chain-termination agents.
8. The composition according to claim 5, further comprising a
catalyst.
9. An article comprising the composition of claim 1.
10. The article of claim 9, selected from the group consisting of
panels, films, sheets, pipes, profiles, and objects obtained by
injection moulding.
11. An object comprising a covering comprising the transparent
protective layer composition of claim 1.
Description
[0001] This application claims benefit, under U.S.C. .sctn.119(a)
of French National Application Number 04.05259, filed May 14, 2004;
and also claims benefit, under U.S.C. .sctn.119(e) of US
provisional application 60/603214, filed Aug. 20, 2004.
FIELD OF THE INVENTION
[0002] The present invention relates to transparent amorphous
polyamides based on diamines and on tetradecanedioic acid.
Advantageously, the diamines are cycloaliphatic diamines. The
present invention also relates to the objects obtained from this
composition.
[0003] Polyamides are polymers which are widely used for their
numerous properties. Specifically, polyamides exhibit some or all
of the properties listed below: transparency, impact, tensile
and/or compressive strength, high resistance to external attacks,
such as cold, heat, chemical agents, radiation, in particular UV
radiation, and others. The arrival has consequently been seen of
objects based on polyamides, such as, for example, spectacle
frames, various housings, motor vehicle accessories, surgical
materials, packaging or sporting goods.
BACKGROUND OF THE INVENTION
[0004] The aim of the invention is to prepare polyamides which have
good mechanical properties of stiffness and of toughness, good
chemical resistance, good stress crack resistance, a high heat
distortion temperature and a low moisture absorption.
[0005] U.S. Pat. No. 2,512,606 discloses transparent polyamides
obtained from methylenedi(cyclohexylamine) (CAS [1761-71-3]) and
from linear dicarboxylic acids comprising from 6 to 10 carbon
atoms. These polyamides do not have a sufficient stress crack
resistance in the presence of alcohols. Furthermore, they can
crystallize under certain conditions and, for this reason, do not
retain their initial transparency. The
4,4'-methylene-bis(cyclohexylamine) or
p-bis(aminocyclohexyl)methane employed in U.S. Pat. No. 2,512,606
is often described under the name of PACM and consists of a mixture
of cis-cis, cis-trans and trans-trans isomers. PACM is typically
obtained by hydrogenation of methylenedianiline (CAS [101-77-9]).
It is available commercially from BASF and Air Products. The
examples in U.S. Pat. No. 2,512,606 use adipic acid or sebacic acid
as linear dicarboxylic acid. Tetradecanedioic acid is not mentioned
among the dicarboxylic acids which can be used.
[0006] Patent Application U.S. Pat. No. 5,360,891 discloses in
particular mixtures of linear dicarboxylic acids and of PACM
comprising from 35 to 60 mol % and more particularly from 45 to
50.5 mol % of trans-trans isomers. Mention is more particularly
made, among the linear dicarboxylic acids, of suberic acid, azelaic
acid, sebacic acid, dodecanedioic acid and tridecanedioic acid.
Sebacic acid and dodecanedioic acid are particularly preferred.
Tetradecanedioic acid is not mentioned. Example 1 of Patent
Application DE 43 10 970 describes a polyamide obtained by
virtually equimolar mixing of PACM (comprising approximately 50 mol
% of trans-trans isomers) and of dodecanedioic acid. This
polyamide, often referred to as Polyamide PACM.12, exhibits, by
differential scanning calorimetry (DSC), a glass transition
temperature of 140.degree. C., a melting point of 248.degree. C.
and a recrystallization point of 180.degree. C. Example 2 of Patent
Application DE 43 10 970 describes a polyamide obtained by
virtually equimolar mixing of PACM and of sebacic acid. This
polyamide, often referred to as Polyamide PACM.10, exhibits, by
DSC, a glass transition temperature of 149.degree. C., a melting
point of 269.degree. C. and a recrystallization point of
180.degree. C.
[0007] The polyamide PACM.12 of Example 1 of Patent Application
U.S. Pat. No. 5,360,891 is available commercially under the name of
Trogamid.RTM. CX7323 from Degussa. The technical documentation of
this product ("Transparent Polyamides with Outstanding Combination
of Properties") clearly indicates the microcrystalline nature of
this polymer. The microcrystallinity of the polyamide PACM.12 can
improve some properties of transparent amorphous polyamides, such
as the resistance to solvents or the stress crack resistance, but
it can also be harmful to the transparency, in particular if the
component based on polyamide PACM.12 is subjected to conditions
which promote recrystallization. The technical documentation of the
polyamide PACM.12 furthermore indicates that Trogamid.RTM. CX7323
absorbs 3.5% by weight of water at 23.degree. C. under saturated
conditions. It is also specified that this water uptake does not
make possible sterilization with steam.
[0008] The publication "Properties of a Polyamide Thermoplastic
Based on 2,2-bis(4-aminocyclohexylpropane)" (Polymer Engineering
and Science, January 1978, Volume 18(1), pp. 36-41) indicates that
homopolyamides based on PACM and on linear dicarboxylic acids, such
as adipic acid, suberic acid, azelaic acid, sebacic acid or
dodecanedioic acid, are opaque and exhibit well defined
crystallization and melting points. In contrast, homopolyamides
based on isopropylidenedi(cyclohexylamine) (CAS [3377-24-0]),
better known under the common name of PACP, with these same acids
are transparent and colourless and do not exhibit, with the
exception of the PACP.10 (sebacic acid) combination, signs of
crystallinity. Tetradecanedioic acid is not mentioned in these
studies.
[0009] Patent Application U.S. Pat. No. 5,696,202; U.S. Pat. No.
5773,558; U.S. Pat. No. 5,886,087; U.S. Pat. No. 6,008,288; And
U.S. Pat. No. 6,277,911 disclose more particularly transparent
amorphous polyamides obtained from
2,2'-dimethyl-4,4'-methylenebis(cyclohexylamine) (CAS [6864-37-5])
and from linear dicarboxylic acids, and their blends or alloys with
homopolyamides. The preferred linear dicarboxylic acids comprise
from 8 (suberic acid) to 12 (dodecanedioic acid) carbon atoms.
Sebacic acid and dodecanedioic acid, and their mixture, are
particularly preferred. Tetradecanedioic acid is not mentioned.
[0010] The 2,2'-dimethyl-4,4'-methylenebis(cyclohexylamine) or
bis(3-methyl-4-aminocyclohexyl)methane employed in U.S. Pat. No.
5,696,202; U.S. Pat. No. 5773,558; U.S. Pat. No. 5,886,087; US
6,008,288; and U.S. Pat. No. 6,277,911 is often described under the
name of BMACM and consists of a mixture of cis-cis, cis-trans and
trans-trans isomers. It is available commercially from BASF under
the name of Laromin C260.
[0011] Example 1 of Patent Application EP 0 725 101 describes a
polyamide obtained by virtually equimolar mixing of BMACM (Laromin
C260) and of dodecanedioic acid. The polymer obtained, often known
as Polyamide BMACM.12, is transparent, exhibits good mechanical
properties and exhibits stress crack resistance in the presence of
alcohols. Its glass transition temperature, measured by DSC, is
157.degree. C. A melting or recrystallization phenomenon is not
observed. Example 2 (comparative) of Patent Application EP 0 725
101 reproduces Example 1 of Patent Application DE 43 10 970 and
confirms the microcrystalline nature of the polyamide PACM.12. The
polyamide BMACM.12 of Example 1 of Patent Application EP 0 725 101
is available commercially under the name of Grilamid.RTM. TR90 from
EMS. The technical documentation of this product ("A Transparent
Polyamide with Unlimited Possibilities") indicates that the
polyamide BMACM.12 exhibits a glass transition temperature of
155.degree. C. and absorbs 3.0% by weight of water at 23.degree. C.
under saturated conditions. It is also indicated that components
made of Grilamid.RTM. TR90 can become hazy (whitening) during
prolonged exposure in water to temperatures of greater than
80.degree. C.
[0012] The abovementioned documents have demonstrated that
transparent amorphous polyamides exhibiting a high glass transition
temperature are known. In some applications, these transparent
amorphous polyamides are used in preference to other transparent
amorphous polymers, such as PMMA (poly(methyl methacrylate)) or PC
(polycarbonate), as they exhibit better resistance to solvents and
to the stress cracking phenomenon.
[0013] A high glass transition temperature makes it possible to
imagine components made of transparent amorphous polyamides which
can function at high operating temperatures, whether for short
periods of time, which reflects the common notion of HDT ("Heat
Distortion Temperature"), or for longer periods of time, which
reflects the common notion of CUT ("Continuous Use Temperature").
However, the abovementioned transparent amorphous polyamides can
absorb up to 3.5% or more by weight of water at 23.degree. C. under
saturated conditions. The water thus absorbed has a well known
plasticizing effect which results, in fact, in a decrease in the
glass transition temperature. It is therefore desirable to have
available transparent amorphous polyamides exhibiting a high glass
transition temperature but having a limited water absorption.
[0014] It has now been found that polyamides resulting from the
condensation of diamines, preferably cycloaliphatic diamines, and
of tetradecanedioic acid or of mixtures of acids comprising at
least 50 mol % of tetradecanedioic acid have all these advantages.
The Applicant Company has discovered that these polyamides are
amorphous and transparent and have good mechanical properties of
stiffness and of toughness, good chemical resistance, good stress
crack resistance, a high heat distortion temperature and a low
moisture absorption.
SUMMARY OF THE INVENTION
[0015] The present invention relates to a transparent amorphous
polyamide which results from the condensation:
[0016] of at least one diamine chosen from aromatic, arylaliphatic
and cycloaliphatic diamines,
[0017] of tetradecanedioic acid or of a mixture comprising at least
50 mol % of tetradecanedioic acid and at least one diacid chosen
from aliphatic, aromatic and cycloaliphatic dicarboxylic acids.
[0018] The invention also relates to a composition comprising, by
weight, 1 to 100% of the preceding polyamide and 99 to 0% of a
semicrystalline polyamide.
[0019] The invention also relates to the objects composed of the
composition of the invention, such as panels, films, sheets, pipes,
profiles or objects obtained by injection moulding.
[0020] The invention also relates to objects covered with a
transparent protective layer composed of the composition of the
invention.
DETAILED DESCRIPTION OF THE INVENTION
[0021] As regards the diamines, they are aromatic, arylaliphatic or
cycloaliphatic in nature and advantageously comprise from 6 to 36
carbon atoms. They can be used alone or as mixtures. A minority of
moles of diamine can optionally be substituted by linear aliphatic
diamines, such as, for example, hexamethylenediamine,
nonanediamine, decanediamine or dodecanediamine, or branched
aliphatic diamines, such as, for example,
methylpentamethylenediamine.
[0022] Among aromatic, arylaliphatic or cycloaliphatic diamines or
their mixtures, arylaliphatic or cycloaliphatic diamines are
preferred. Mention may be made, among arylaliphatic diamines, of,
for example, meta-xylylenediamine.
[0023] Among arylaliphatic or cycloaliphatic diamines comprising
from 6 to 36 carbon atoms or their mixtures, cycloaliphatic
diamines are preferred. Non limiting examples of cycloaliphatic
diamines and their processes of preparation are indicated in the
publication "Cycloaliphatic Amines" (Encyclopaedia of Chemical
Technology, Kirk-Othmer, 4th Edition (1992), pp. 386-405). These
diamines often comprise several isomers because of the nature of
the industrial manufacturing processes. Commercially available
cycloaliphatic diamines often comprise one or two optionally
substituted cycloaliphatic rings. Mention may be made, among
cycloaliphatic diamines comprising a cycloaliphatic ring, of, for
example, isophoronediamine (CAS [2855-13-2]),
1,4-cyclohexanediamine (CAS [3114-70-3]) or
1,3-diaminomethylcyclohexane (CAS [2579-20-6]).
[0024] Cycloaliphatic diamines comprising two cycloaliphatic rings
are preferred in this application. These diamines correspond to the
general formula (I) 1
[0025] in which
[0026] R1 to R4 represent identical or different groups chosen from
a hydrogen atom or alkyl groups of 1 to 6 carbon atoms and X
represents either a single bond or a divalent group composed:
[0027] of a linear or branched aliphatic chain of 1 to 10 carbon
atoms,
[0028] of a cycloaliphatic group of 6 to 12 carbon atoms,
[0029] of a linear or branched aliphatic chain of 1 to 10 carbon
atoms substituted by cycloaliphatic groups of 6 to 8 carbon
atoms,
[0030] of a group of 8-12 carbon atoms composed of a linear or
branched dialkyl with a cyclohexyl or benzyl group.
[0031] PACM, PACP and BMACM have already been mentioned among
cycloaliphatic diamines comprising at least two cycloaliphatic
rings. Mention may also be made of the diamines
bis(3,5-dialkyl-4-aminocyclohexy- l)methane, -ethane, -propane or
-butane. These diamines and their process of preparation are
disclosed in U.S. Pat. No. 4,293,687.
[0032] As regards the tetradecanedioic acid (or its anhydride), the
processes for producing this acid (or its anhydride) do not form
part of the subject-matters of the invention. One method for
producing linear dicarboxylic acids consists of the biofermentation
of alkanes or of corresponding alkyl esters. This technology is
used by Kaleys (formerly Cathay Biotechnology Company), which sells
linear dicarboxylic acids comprising from 9 to 18 carbon atoms.
Tetradecanedioic acid (or its anhydride) is available commercially
from this company.
[0033] Tetradecanedioic acid can be replaced in a proportion of at
most 50 mol %, preferably 30 mol %, by other aliphatic, aromatic or
cycloaliphatic dicarboxylic acids or their mixtures. Mention may be
made, among other aliphatic dicarboxylic acids, of, for example,
linear or branched acids comprising from 6 to 20 carbon atoms and
in particular adipic acid, suberic acid, azelaic acid, sebacic acid
or dodecanedioic acid. Mention may be made, among optionally
substituted aromatic dicarboxylic acids, of, for example,
isophthalic acid, terephthalic acid or naphthalenedicarboxylic
acid. Mention may be made, among optionally substituted
cycloaliphatic dicarboxylic acids, of, for example,
cyclohexanedicarboxylic acid.
[0034] As regards the blends of the preceding polyamide with a
semicrystalline polyamide, mention may be made, as example of
semicrystalline polyamide, of polyamides based on
hexamethylenediamine (PA 6-9, 6-10, 6-12, 6-14), on nonanediamine
(PA 9-10, 9-12, 9-14), on decanediamine (PA 10-10, 10-12, 10-14),
on dodecanediamine (PA 12-10, 12-12, 12-14), and PA 10, PA 11 and
PA 12. Mention may also be made of copolyamides 11/12 having either
more than 90% of 11 units or more than 90% of 12 units. These
polyamides result from the condensation of 11-aminoundecanoic acid
with lauryllactam (or C.sub.12 .alpha.,.omega.-amino acid). The
blend can be produced in the molten state in the usual devices,
such as, for example, an extruder. A catalyst can be added. This
can also be the remnant of the optional catalyst used for the
preparation of the amorphous polyamide or for the preparation of
the semicrystalline polyamide. This is advantageously an organic or
inorganic catalyst and this is preferably phosphoric acid or
hypophosphoric acid. The amount of catalyst can be up to 3000 ppm
with respect to the weight of the amorphous polyamide and of the
semicrystalline polyamide and advantageously between 50 and 1000
ppm. Such catalysts are disclosed in Patent EP 550 308.
[0035] As regards the preparation of the polyamides of the
invention, use may be made of any conventional process for the
synthesis of polyamides and copolyamides by condensation of the
corresponding monomers. The synthesis can be carried out in the
presence of a catalyst. This is advantageously an organic or
inorganic catalyst and this is preferably phosphoric acid or
hypophosphoric acid. The amount of catalyst can be up to 3000 ppm
with respect to the weight of the amorphous polyamide and
advantageously between 50 and 1000 ppm. The transparent amorphous
polyamides according to the invention and their blends or alloys
with one or more other polyamides can also comprise additives.
Mention may be made, as example of additives which can be used, of
reinforcing or non-reinforcing fillers, heat or UV stabilizers,
internal or external lubricants, plasticizers, flame retardants,
pigments and dyes, conductive or static-dissipative fillers, impact
modifiers or chain-termination agents.
[0036] The transparent amorphous polyamides according to the
invention and their blends or alloys with one or more other
polyamides can be processed by known technologies for the
conversion of thermoplastics, such as, for example, injection
moulding or coinjection moulding, the extrusion of sheets, films,
panels, profiles, filaments, pipes or tubing, or the extrusion-blow
moulding of flasks, bottles or tanks. The objects which can be
produced according to these technologies are also a subject-matter
of the invention.
EXAMPLES
Examples 1, 2 (Comparative), 3 and 4 (According to the
Invention)
Example 1
[0037] The following monomers are introduced into a reactor
equipped with a stirrer: 13.76 kg (57.82 mol) of Laromin 260 (BMACM
supplied by BASF), 11.47 kg (56.7 mol) of sebacic acid, 25.2 g of
phosphoric acid and 505 g of H.sub.2O. The mixture thus formed is
placed under an inert atmosphere and is heated until the
temperature reaches 280.degree. C. and 20 bar of pressure. After
maintaining for 2 h, a pressure-reducing operation is subsequently
carried out for 1 h to return to atmospheric pressure. The
polycondensation is continued at 280.degree. C. for approximately 2
h while flushing with nitrogen until the desired viscosity of the
polymer is achieved. The final product has an intrinsic viscosity
of 1.2 dl/g.
Example 2
[0038] Example 1 is repeated with the following monomers introduced
into a reactor equipped with a stirrer: 13.52 kg (57.79 mol) of
Laromin 260 (BASF), 13.18 kg (57.22 mol) of dodecanedioic acid
(from Cathay Biotechnology, with a very high purity of >99%),
26.7 g of phosphoric acid and 534 g of H.sub.2O.
Example 3
[0039] Example 1 is repeated with the following monomers introduced
into a reactor equipped with a stirrer: 12.0 kg (50.4 mol) of
Laromin 260 (BASF), 13.0 kg (50.4 mol) of tetradecanedioic acid, 25
g of phosphoric acid and 500 g of H.sub.2O.
Example 4
[0040] The following monomers are introduced into a reactor
equipped with a stirrer: 12.67 kg (53.22 mol) of Laromin 260
(BASF), 5.05 kg (25 mol) of sebacic acid and 7.28 kg (28.23 mol) of
tetradecanedioic acid, 25 g of phosphoric acid and 500 g of
H.sub.20.
[0041] The results of the tests are found in the following TABLE
1:
1TABLE 1 Intrinsic Water uptake Water uptake viscosity Tg (after 13
days) (after 43 days) Ex. Description in dl/g (.degree. C.) (% by
weight) (% by weight) 1* BMACM.10 1.21 165 3.4 3.8 2* BMACM.12 1.19
156 2.6 2.9 3** BMACM.14 1.16 146 2.2 2.4 4** BMACM.14/ 1.18 157
2.5 2.8 BMACM.10 *Comparative **According to the invention
Example 5
[0042] The following monomers are introduced into a reactor
equipped with a stirrer: 12.7 kg (60.58 mol) of PACM (sold under
the name PACM20 by Air Products) and 15.63 kg (60.58 mol) of
tetradecanedioic acid, 28.3 g of phosphoric acid and 566 g of
H.sub.2O.
2TABLE 2 Intrinsic Water uptake Water uptake viscosity Tg (after 13
days) (after 43 days) Ex. Description in dl/g (.degree. C.) (% by
weight) (% by weight) 5** PACM.14 1.20 129 2.2 2.7 **According to
the invention
[0043] The intrinsic viscosities, measured in meta-cresol, were
recorded according to the ISO 307 (1994) method at 20.degree. C.
The values of the water uptake at 23.degree. C. by immersion in
water were obtained according to the ISO 62 (1980) method on
samples with a thickness of 1 mm. The glass transition temperatures
were measured by DSC according to the ISO 11357-3 (1999)
method.
3 TABLE 3 Flexure Tensile ISO 178, Charpy impact ISO 527, DIN
53455, ASTM 638 DIN 53452, ISO 179, DIN 53453 Modulus Stress Stress
ASTM 790 With With of at yield Elongation at break Elongation
Modules of notch notch Elasticity In at yield In at break
Elasticity (23.degree. C.) (-40.degree. C.) Reference in MPa MPa in
% MPa in % in MPa In KJ/m2 In KJ/m2 Ex. 3** 1360 50.8 6 45.5 180
1400 11 8.3 according to the invention Ex. 5** 1400 49.5 6 46.8 170
1420 8.9 6.39 according to the invention
* * * * *